Lubricating oil compositions and additives for lubricating oils



LUBRECATING E QG l /EPQSHEQNS AND ADDI- TlVlES FQR LUEEICATWG 8H5 RudolfKern, Neustadt (Haardt), and Hans Scheurer,

Schlierbaeh (Neekar), Germany, assignors to Rhein- Chemie G. m. b. El,Mannheim-Rheinaa, Germany, a corporation of Germany No Drawing.Application .luly 6, 1954. Serial No. 441,664

Claims priority, application Germany July 7, 1953 '7 Claims. (Cl.252-333) The present invention relates to new compositions productssuitable for lubricating purposes as well as compositions suitable asadditives for lubricating oils.

Oil-soluble salts of sulphonic acids have been added to mineral oils,especially to motor lubricating oils, in order to keep in dispersion theresinous, asphaltic-, and cokelike products formed during the operationof the motor, and thus to prevent the precipitations from causingtrouble in the motor. Numerous sulphonates are either soluble withdifficulty or even immiscible in hydrocarbon oils, while others arereadily soluble. Finally, there are those which only swell to a certaindegree. In View of these different physical properties, only a smallpart of the numerous sulphonates may be added to the hydrocarbon oils inthe desired amount.

Whereas the copending application, Serial No. 346,784, relates to amethod of forming liquid hydrocarbon oil solutions of naphthenic acidsalts, the present inven ion relates to similar methods wheresurface-active s phonates of various kinds may be added to hydrocarbonseven in a higher form of concentration without impairing the desiredproperties of the mixtures.

A further object of the present invention consists in improving theproperties of the sulphonates desired in motor oils by supplementingtheir dispersing action by an improved detergent effect.

It is another object of the present invention to produce highlyqualified motor oil additives which are easily soluble and form verystable solutions without any special apparatus or other means beingrequired therefor.

According to the invention it has been found that sulphonates are moreeasily dissolved and mixed with lubricating oils if polyalk 'leneglycolderivatives as well as higher boiling monc-ethers are being addedthereto. Furthermore it has been found that the properties of thelubricating oils obtained by such additions comply with the highestrequirements of oils for internal combustion engines insofar as theirlubricating qualities as well as their chemical and physical stabilityis concerned. Therefore, the incorporation of sai compounds inlubricating oils as prescribed by the invention is also advantageous inthose cases in which the dissolv ng culties described above exist onlyin a ext .t, or not at all. This underlines the expediency ofincorporating s-'.1l phonates in motor lubricating in general incombination with polyallzyleneglycol derivatives and higher boilingethers.

The term sulphonates as it is being used herein refers to any salts ofsurface active sulphonic aci s, and p ticularly polyvalent metal saltsof such sulohonic acids, Examples of such salts are so donates of lineearths, such as calcium, barium, stron um, l'llflgllicllllfi, as well assulphonates of lead, zinc, aluminum, chromium, nickel, copper, tin, andcadmium. Also alkali and ammonium salts may be used.

The following are examples of chic acids suitable for this purpose:Sulphonic acids wh .h are obtained by refining petroleum distillate withsulphuric acid, such as Fatented Sept. 2, 1958 ice in which R representsan alkylene radical having 2 or 3 carbon atoms, 11 represents a wholenumber up to 20. preferably from 2 to 7, one of the groups X and Y isselected from the class consisting of hydrogen, alkyl-, aryl-, aralkyl-,alkaryl-, alicyclic and acyl-radicals, while the other is selected fromthe class consisting of allryl-, aryl-, aralkyl, alkaryl-, alicyclic andacyl-radicals having more than 6 and preferably more than 8 carbonatoms.

Examples for hydrocarbon radicals with more than 6 carbon atoms are thefollowing: 2 ethylhexyl-, n-octyl-, dodecyl-, tetradecycl-, octadecyl-,and octadecenyl-radical; further alkyl-radicals of those alcohols whichare obtained by hydrogenation of natural or synthetic fatty acids whichare produced by reduction of carbon monoxide under normal or increasedpressure by the oxosynthesis or by the oxidation of paraffin Wax;furthermore, the phenyl-, dibntylphenyl-, dodecylphenyb, naphthyl-,heptylnaphthyl-, hexadecylnaphthyl-, benzyl-, phenylethyl-,phenyloctadecyl-radical, etc; also the methylcyclohexyl-,butylcyclohexyl-, naphthenyl-radical, etc.; as well as perhydrogenatedderivatives of monoor polysubsti tuted alkylor aralkylphenols ornaphthols. Among acylradicals, the acid groups of the following carbonicacids will be applicable: Capronic acid, caprinic acid, laurinic acid,myristinic acid, oleic acid, rapeseed fatty acid, castor oil fatty acid,oxystearic acid, fatty acids obtained by the oxidation of paraffin wax,benzoic acid, benzylbenzcic acid, alkylbenzoic acid, phthalic acid,naphthenic acid, phenyl-stearic acid, oxyphenylstearic acid, etc.

The following compounds are examples for those corresponding to thegeneral formula stated above, and are mentioned only for the purpose ofillustration, and therefore are not to be regarded as a limitation as tothe compounds which may be used:

Dodecylphentaethylene glycol, octadecenyl-hexaethylene glycol,2-ethylhexyl-pentaethylene glycol, nonylbeptaethylene glycol,phenyl-ethyl-pentaethylene glycol, methyl-cyclohexyl-octaethyleneglycol, p-octylphenyltetrapropylene glycol, dodecylcyclohexapropyleneglycol, hexylnaphthyltetra-ethylene or propylene glycol; furthermore,dodecylor lanryl-pentaethyleneglycohnethyl ether (the erm lauryl is tobe understood as designating the radical from fatty alcohol producedfrom coconut fatty acids),p-methyl-cyclohexyl-tetraethyleneglyccl-octyl-ether,p-octylphenyl-tetraethylene-glycol-isopropylether,octadecenyl-hexaethylene-glycol-phenylethyl--etber,octadecyldiolpentaethylene-glycol-isopropylether, 2ethylhexyl-heptaethylenegl; colether, etc;dodecylbenzyl-pentapropyleneglycol-oleate,benzoylpentaethyleneglycol-oleate, benzoyl-heptaethyleneorpropylene-glycol-butylether, pentaethyleneglycol-monoste it isunderstood that in lieu of 21 vates, mixtures thereof may also be used.

The viscosity-reducing eflec: oi polyalkyleneglycol derivatives uponsolutions of sulphonates in hydrocarbon oils may be demonstrated by amodel using turpentine substitute. The following experiment was carriedparts by weight-of barium salt of apetroleumsulphonic acid could only bedissolved with difficulty in 100 parts by weight of a technical testgasoline (turpentine substitute) having'a flas'h point-higher than-21 C.and with 18% of aromatics. The solution had a viscosity'of 90.65 cat. at50 C. However, the same ingredients were easily dissolved" in thepresence 'of 4 parts of a reaction product of 1 mol. of oleinalco'holwith l'5 inol. of ethyleneoxide. The solution thus formed 'had-aviscosity of 1.33 -cst. at 50 C. A'correspondingreduction in viscositywas obtained with a reaction-product of 1 mol. of decylalcohol with 2.2molJofethyleneoxide.

In addition to the polyalkyleneglycolderivatives, the invention further'includ'es the use of higher boiling ethers comprising at least oneradical with more than 6 -carb'on atoms. The presence of such ethers inthe mixtures improves their storage'sta'bility. Theseethers are alsogood solvents and softening agents for resinification and otherdecomposition products or the liquidhydrocarbon :oils formed during thecombustion process.

The extraordinary chemical and physical resistance of the etherstructure'rendersthe ethers much superior 'to esters, already proposedfor'the same purpose.

It should be noted, thatit is important'to select such ethers, thevolatility of which is' sufiicientlydoweven at higher temperatures andwhich, on the other'handgremain liquid at room temperature andeven atlower outside temperatures in wintertime.

In comparison with the above-mentioned polyalkylencglycol-alkyl-ethers,the high boiling'ethers dealt with in the last paragraphs are distinctlydifferent in so far as they contain only one, and no more than two,"oxygen atoms which have ether-like linkages within the molecule, andthus are free of polyalkylene-glycol groups.

The high boiling ethers may be either of symmetrical or unsymmetricalstructure, and they may be used either singly or in a mixture of two ormore.

The following are examples of high boiling ethers according to thepresent invention. It is to be understood that these are illustrativeonlyof the numerous compounds which may be used. Specific compounds tobe mentioned are:

Di-n-hexylether, di-n-octylether, di-n-nonylether, di-2-ethyl-hexylether, lauryl-2-ethylhexylether, -octadecen-9-yl-l-isobutylether, butandiol-(1,3)-monoctylether, butandiol (1,4)isobutyldodecylether, lauryl-cyclohexylether,nonyl-4-methylcyclohexylether, nonylbenzylether,tetrahydro-naphthylrnethyl-2-ethylhexylether, 'dodecylphenylether,octyl-B-tetralolether, 4-octylphenyl-Z-ethylhexylether, etc.;octadecenyl-4-methylbenzylether, tetrahydronaphthylmethyl-phenylor'benzyl-ether, dibenzylether, and butandiol-( 1,4) -dibenzylether.

Ethers from paraffin fatty alcohols or their first runnings, as well asthe oxoor naphthentic alcohols are particularly suitable. derstood asmeaning the first distillate of a mixture 'of'alcohols obtained fromhigh pressure hydrogenation of paraffin fatty acids wherein the alcoholsof the mixture have a chain length of 6-9 carbon atoms.

Naphthenic acids as obtainable by raffination of mineral oils may betransformed into the corresponding naphthenic alcohols by high pressurereduction or by the process of Bouveault-Blanc. These alcohols may beeasily reacted to form ethers, as, for instance, dinaphthenylether,naphthenyl-benzyland -2-ethylhexylether.

Solutions of sulphonic acid salts in hydrocarbons according to theinvention may be produced in any desired order of succession, and maythus be adapted to the requirements in each particular case. Thus, amixture of sulphonate with one or more of the inventive additions may beadded to a hydrocarbon or a hydro-carbon 'oil.

The term first running is to be un- Also, it is possible to incorporatethe inventive additions to a solution, a gel, or a suspension ofsulphonates in hydrocarbons. The sulphonic acid salt mayalso be added toa solution of the inventive additions in hydrocarbons in thesame manneras mixtures of sulphonates withhydrocarbons, on the one hand, and of theinventive additions with hydrocarbons, on the other hand, may bedissolved within each other. "Often it is recommendable to carryout themixing at higher temperatures of,.for example, 50 to 250 C., andpreferably between and 200 C. When speaking herein of'inventiv eaddition, both the polyalkyleneglycol derivatives, as well as the higherboiling ethers, both of which have been previously mentioned, are to beincluded, either individually or combined.

The lubricating oils compounded-as above described may, according toEan'othcr feature of the invention, be further improved by the additionof naphthenates. The difficultics in 'dissolv'ingthem'do not occur inmixtures of the polyalkyleneglycol derivatives and higher boilingethers. These naphthenates, and especially the basic alkaline earthnaphthenates, also contributein themixture according to the invention toan improved detergent, dispersing, and neutralizing effect.

Finally, in some cases it is advisable to'add inhibitors to theadditiveor the lubricating oils in'a manner known as such.

For practical reasons it is most advisable-to'realize the invention byproducing a mixture of "salts of the surface-active sulphonic acids,the-etherized and/or ester'ized polyalkleneglycol derivatives and thehigher boiling ethers without the polyglycol group. Sucha mixture formsa so-called additive, a suitable amount of which should be added in eachrespective case to the particular motor oil in question. When usingsuchadditives, it has been found that a content in the higher boiling ethersimproves the miscibility of the" additive with the basic oilextraordinarily. Asutricient amount of polyalkyleneglycol derivativesand higher boiling ethers readily permits the additive which'conta'ins'normally oil-insoluble sulphonates, to dissolve ain 'a basic oil at roomtemperature without any stirring apparatus.

The required amount in polyalkenyleneglycol 'derivatives may vary withinwide limits, for example, from one percent by weight relative tosulphonate to "equal parts by weight or more. The particular amount --to'be added depends upon the 'kind of sulp'honate applied, the kind ofhydrocarbons used, and the desired viscosity of the solution or thedegree of the desiredimpr'ovement of a motor oil..

Generally speaking, motor oils will be improved sufficiently by anaddition of 2 to 7% of an additive consisting of the inventivecombination of the mentioned additions. Very often an addition of 1%will be found to 'suflice, whereas in certain special cases up to 25% ormore of such an additive will be of advantage.

The following examples may further elucidate the invention without,however, limiting the scope thereof.

EXAMPLE 1 From the watery solution of the sodium salt of a pctroleumsulphoacid with the average molecular weight of 325 to which calciumchloride was added, the corresponding calcium salt was produced. Afterdrying the same, an attempt was made to dissolve 10 parts of thiscalcium salt at a temperature of 100 to C. in 200 parts by weight of alubricating oil of a specific gravity at 20 C. of 0.882, a viscosityindex of 81, a coking number according to Conradson of 0.11, and-withoutany gasoline-insoluble constituents. After cooling, however, a partialseparation of the calcium salt again occurred.

If, however, 10 parts of the calciumpetroleumsulphonate are beingstirred up with 10 parts oleylheptapropyleneglycolether and 10 parts ofhexadecylhexylether, such mixture could be easily dissolved in 200 partsof the lubricating oil. This solution when cooled remained absolutelyclear.

EXAMPLE 2 The calcium salt was formed of a Twitchell sulphonic acidwhich had been obtained in a known manner by a sulphonizing condensationof 1 mol. of oleic acid, 1 mol. of naphthalene, and 6 mol. of fumingsulphuric acid. 30 parts of such calcium salt, which otherwise ispractically oil-insoluble, were stirred at 90 C. into a mixture of 650parts of a parafiin base motor oil having a viscosity of 61 est. 50 C.,viscosity index of 100, 30 parts of octadecenylhexapropyleneglycoletherand five parts of di-tert.-butyl-p-cresol as an inhibitor. A motor oilwas thus formed of high lubricating quality which strongly suppressesthe normal wear and tear of the engine as compared with analogous oils.Furthermore, when such compounded oil was in use, it had a strongdispersing effect upon residues of combustion.

EXAMPLE 3 In 20 parts of cocolaurylpentaglycolether and 27 parts oflaurylethylhexylether were dissolved under stirring and heating up to150 C.:

35 parts bariummononaphthenate and 15 parts bariumalkylbenzolsulphonate,

wherein the alkyl radical corresponded to a chain with 14 C-atoms.Thereafter,

3 parts of di-tert.-butyl-p-cresol were added.

parts of this mixture were added to 95 parts of a basic oil which hadbeen produced by a suitable mixture of Brightstoclo, machine-, andspindle-oils and had the following characteristics:

Density at 20 C 0.905 Solidifying point C 37 Viscosity at 50 C cst 44.9Viscosity ind x 73 Coke constituents according to Conradson percent 0.2;

This oil mixture was subjected to a practical test in a passenger car, aMercedes-Benz Model 170 V. Before the test, the pistons were removedfrom the engine and completely cleaned. The test run extended over 5500km. during which the oil was changed at 500, 1500 and 3500 km.

At the end of the test run, the pistons had a perfect metallicappearance, all rings moved freely, and only small sludge traces showedin the piston ring grooves.

EXAMPLE 4 5% of an additive consisting of was dissolved in the oildescribed in detail in Example 3 and subjected to a practical test in apassenger car of the Volkswagen type, wherein the test conditions andoil change periods were the same as mentioned in Example l. Also in thiscase, all piston rings were found to be freely movable after the test.However, as compared with Example 3, the ring grooves were practicallyspotless, whereas parts of the piston skirt and the inside of the pistonlooked darker.

s EXAMPLE 5 For comparing the stability in storage of compounded oils,the lubricating qualities of two oils were measured on an Almen-Wielandapparatus. This well-known testing apparatus substantially consists oftwo halves of a bearing bushing which embrace a revolving shaft under agradually increasing pressure. This rather complicated machine isdesigned so that every feature or characteristic of the object to betested is carefully considered. Thus, for example, a recordedmeasurement may be obtained of the load to which the bearings may besubjected until they are welded together with the shaft.

Two differently compounded oils were storedin vessels of larger size. Atintervals of several days, specimens were simultaneously withdrawn fromboth oils from the top as well as from the bottom for determining thelubricating qualities.

A basic oil with the following characteristics:

20 0.923. Viscosity at 20 C 460 cst. Viscosity at 98.9 C 10 est.Viscosity ndex 1 44. Solidifying point 19 C. Flash point 237 C., and

Coking residue according to Conrads0n 0.60%.

was mixed with 5% of an additive containing, aside from unsaponifiableorganic compounds containing phosphorous and sulphur, an oil-solublebariumpetroleumsulphonate in which the molecular weight of the acid wasapprox. 300. The additive had 10.5% of ash, 12.1% of sulphate ash, Ba5.6%, S 4.4%. The compounded oil showed the following lubricating valuesin accordance with the storage periods mentioned:

Oil from Oil from the top, the botkg. tom, kg.

2 days 750 1, 150 7 day 550 700 EXAMPLE 6 The quality of the motor oilsas improved according to the invention was likewise determined on thetest stand which consisted primarily of a one-cylinder, 12 H. P. dieselengine, Model KDW 415 E, made by the Motoren- Werke Mannheim, and which,for measuring the output, was coupled with an electric generator. Foreach test run, the engine was provided with new pistons and new cylinderliners. Before each test run, the engine was tuned up by running it for6 hours with the particular oil in question. Before the actual test run,the oil was removed and the piston once more taken out and examined. Thetest run lasted hours and 60 hours, respectively, under full load.During this time, all necessary data was determined, such as the output,the fuel consumption, the temperatures of the oil which were heldconstant by means of a thermostat, the cooling water and the exhaustgases, etc. After the test run, the pistons, bearings, etc. wereexamined, and the difference in weight of the piston rings before andafter each test run was de- 4 termined. Furthermore, the qualities ofthe oil were examined before, during, and" after the test run:

The examples described as-follows were-'carried-out with afuel from theMiddle East having 0.96% sulphur, and a paraffin baseoil S. A. E. 30with a Viscosity at 20C. of 330 cst.

Viscosity at 98.9" C. of 11 cstr Viscosity index of 91.

Density at 20 C. of 0.889.

solidifying point of 24 C.

Flash point of 242 C. 7 Ash,- acidity, and saponifi'cation degree-ofCoking residue accordingtoConradson of- 0.04%.

To this oil'were added or eachof the following. additives:

parts of:oleinalcoholsulphuric acid ester,

parts of naphth'e'riic acid,

675 parts of-Ba( OH) .8H O,

parts of an oxeth'ylation product of 1 mol.' of technical" laurylalcoholwith 90% dodecylal'coholfand' 10%1 of? higher boiling fatty alcoholsplus smelf of ethyleneoxide,

25 parts of lauryletliylh'exylether, and

3 parts of ethylhexylphenol;

20 parts of barium saltfofla; monoalkylbenzolsulphouic acid(moleculanweight approx; 360-) 30 parts of bariurndinaphtlienate;

30 parts of an ox'ethylationproduct oil 11 mol... of tech'inicallaurylalcohol wit-hit 90%: of: dodecylalcohol-L and: 10% ofhigher-boiling fatty alcohols plus 5 mol. of ethyleneoxide,

17"p'arts'of dodecylethylhexylether, and

3 parts of ethylhexylphenol.

The results attained from the additives (a) and (b-),-

respectively, were as follows: 7

Length of time of the actual 120.

test run. Average driving load 102%r -r 93%. Average fuel consumption'185'g./H. Rm. .lir. QOOgJ/H. P-efljllh Average exhaust temperature 449O; 452 C.

Piston ring wear:

First Ring Second Ring J 7 Third Ring Lulinlricating capacity of theBefore the test run After the test run (Measured on the Almen-Wielandmachine and stated in load in kg. up' to Welding together with testbear-- mg.

Viscosity of the compounded Lubricating Oil measured' at 989 Before thetest run- After the test run Viscosity inde'x Before the test run. Afterthe test run 11.05 'cst 12.80 est Movability ofthering sa; 10. 0 10,0Deposit in the-ring grooves; 8. 1 9. 6 Depositin the grooves of the oilcontrol ring 10.0 9. 9 Deposit'ln'th'e slots'of theoil control ring' 10;0 10.0 Metallic appearance of the outside of the piston 94 9. 6 Metallicappearance of the inside of the piston 101 O 9. 8

wherein R is an' alkylne radical having a minimum of 2 and a maximumof'3carbonatoms, n is a' w'hole number betweenil and 20 and Y is an alkylradical having at least 12 carbon atoms, and a high boiling-mono etherhaving a total of at least 12 carbon atoms and at least one of theradicalsof whichhas more than 6' carbon atoms, said polyalkylene glycolderivative being present in. anv amount of 1% to equal the weight ofsaid sulfonic acid-salt and said polyalkylne glycol derivative and saidhigh boiling other being present-in an amount suffi cient to causedissolution of said'sulfonic acid salt in a lubricating oil.

deposition of resins,-lasp'halts and carbon in'the'oil, at least onepolyalkyleneglycol derivative having the following general formula:

whereitTRisan alkylene'radical having'a' minimum of 2'and' a maximum. of3"carb'on atoms, n'is'a whole inum= ber'between land 20, and wherein oneof the groups X andY is hydrogen and the other of said groups X and Yis"s'electedffon1" the class consisting of alkylnar'yl, aralkyl;alkaryha'ndacylradicals havingat least 6 carhon atoms, aH'd Hf lEE I St1 high boiling mono etherhaving a total of at least 12 carbon atoms andat least one of the radicals of which has at least 6 carbon atoms, saidpolyalkylene glycol derivative being-present in an amount of 1% to equalthe weight of saidsulfonic acid salt and said sulfonic acid salt, saidpolyalkylene glycol derivative and higlr boilingwether being present inan amount of 125% of said product and in an amount suflicient of saidpolyalkylene glycol derivative and said high boiling ether to forma'solution of said sulphonic acid salt in said lubricating. oil.

3; A- new product consisting essentially'ofahydro carbon lubricatingoillhaving dissolvedthere'in atleast one metal salt of a-surfaceactivesulphonic acid of at least 8 carbon atoms -in an amount sufficienttoprevent deposition of resins, asphaltsand carbon in the oil, atleast-onep'olyalkylene glycol derivative having the following'generalformula:

X and Yis hydrogen and the other of'said groups Xand' Y is selected fromthe classconsisting of alkyl, aryl,

aralkyl, alkaryl and acyl radicals having at least 6 carbon atoms in anamount of 1% to equal the weight of said sulphonic acid salt, and atleast 1 high boiling mono ether having a total of at least 12 carbonatoms and at least one of the radicals of which has at least 6 carbonatoms, said sulfonic acid salt, said polyalkylene glycol derivative andsaid high boiling ether being present in an amount of 27% of saidproduct and in an amount suflicient of said polyalkylene glycolderivative and said high boiling ether to form a solution of saidsulphonic acid salt in said lubricating oil, said polyaikylene glycolderivative and said high boiling ether being present in an amount of1-25 of said product.

4. A new product consisting essentially of a hydrocarbon lubricating oilhaving dissolved therein at least one metal salt of a surface activesulphonic acid of at least 8 carbon atoms and at least one salt of anaphthenic acid in an amount suflicient to prevent deposition of resins,asphalts and carbon in the oil, at least one polyalkylene glycolderivative having the following general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of3 carbon atoms, 11 is a whole number between 1 and 20, and wherein oneof the groups X and Y is hydrogen and the other of said groups X and Yis selected from the class consisting of alkyl, aryl, aralkyl, alkaryland acyl radicals having at least 6 carbon atoms, and at least 1 highboiling mono ether having a total of at least 12 carbon atoms and atleast one of the radicals of which has at least 6 carbon atoms, saidpolyalkylene glycol derivative and said high boiling ether being presentin an amount sufficient to form a solution of said sulphonic acid saltand said naphthenic acid salt in said lubricating oil and to maintainsaid sulphonic acid and naphthenic acid salts in solution, therebyincreasing the dispersing power for resins, asphalts and carbon of saidsulphonic acid and naphthenic acid salts.

5. A new product consisting essentially of a hydrocarbon lubricating oilhaving dissolved therein at least one alkaline earth salt of a surfaceactive sulphonic acid of at least 8 carbon atoms in an amountsufi'icient to prevent deposition of resins, asphalts and carbon in theoil, at least one polyalkylene glycol derivative having the followinggeneral formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of3 carbon atoms, 11 is a whole number between 1 and 20, and wherein oneof the groups X and Y is hydrogen and the other of said groups X and Yis selected from the class consisting of alkyl, aryl, aralkyl, alkaryland acyl radicals having at least 6 carbon atoms, and at least 1 highboiling mono ether having a total of at least 12 carbon atoms and atleast one of the radicals of which has at least 6 carbon atoms, saidpolyalkylene glycol derivative being present in an amount of 1% to equalthe weight of said sulfonic acid salt and said sulfonic acid salt, saidpolyalkylene glycol derivative and high boiling ether being present inan amount of 125% of said product and in an amount sufficient of saidpolyalkylene glycol derivative and said high boiling ether to form asolution of said sulphonic acid salt in said lubricating oil.

6. A new composition of matter suitable as an additive for hydrocarbonlubricating oils, said composition consisting essentially of at leastone metal salt of a surface active sulphonic acid of at least 8 carbonatoms, at least one polyalkylene glycol derivative having the followinggeneral formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of3 carbon atoms, n is a whole number between 1 and 20, and wherein one ofthe groups X and Y is hydrogen and the other of said groups X and Y isselected from the class consisting of alkyl, aryl, aralkyl, alkaryl andacyl radicals having at least 6 carbon atoms, and at least 1 highboiling monoether having a total of at least 12 carbon atoms and atleast one of the radicals of which has at least 6 carbon atoms, saidpolyalkylene glycol derivative being present in an amount of 1% to equalthe weight of said sulfonic acid salt and said polyalkylene glycolderivative and high boiling ether being present in an amount sufiicientto cause dissolution of said sulphonic acid salt in a hydrocarbonlubricating oil.

7. A new composition of matter suitable as an additive for hydrocarbonlubricating oils, said composition consisting essentially of at leastone metal salt of a surface active sulphonic acid of at least 8 carbonatoms, at least one salt of a naphthenic acid, at least one polyalkyleneglycol derivative having the following general formula:

wherein R is an alkylene radical having a minimum of 2 and a maximum of3 carbon atoms, n is a whole number between 1 and 20, and wherein one ofthe groups X and Y is hydrogen and the other of said groups X and Y isselected from the class consisting of alkyl, aryl, aralkyl, alkaryl andacyl radicals having at least 6 carbon atoms, and at least 1 highboiling monoether having a total of at least 12 carbon atoms and atleast one of the radicals of which has at least 6 carbon atoms, saidpolyalkylene glycol derivative being present in an amount of 1% to equalthe weight of said sulfonic acid salt and said polyalkylene glycolderivative and high boiling ether being present in an amount sufficientto cause dissolution of said sulphonic acid salt and said naphthenicacid salt in a hydrocarbon lubricating oil.

References Cited in the file of this patent UNITED STATES PATENTS2,565,403 Sproule et a1 Aug. 21, 1951 FOREIGN PATENTS 676,625 GreatBritain July 30, 1952

4. A NEW PRODUCT CONSISTING ESSENTIALLY OF A HYDROCARBON LUBRICATING OILHAVING DISSOLVED THEREIN AT LEAST ONE METAL SALT OF A SURFACE ACTIVESULPHONIC ACID OF AT LEAST 8 CARBON ATOMS AND AT LEAST ONE SALT OF ANAPHTHENIC ACID IN AN AMOUNT SUFFICIENT TO PREVENT DEPOSITION OF RESINS,ASPHALTS AND CARBON IN THE OIL, AT LEAST ONE POLYALKYLENE GLYCOLDERIVATIVE HAVING THE FOLLOWING GENERAL FORMULA: